Show simple item record

dc.contributor.authorKonu, Jari
dc.contributor.authorChivers, Tristram
dc.contributor.authorTuononen, Heikki
dc.date.accessioned2015-11-24T07:37:45Z
dc.date.available2015-11-24T07:37:45Z
dc.date.issued2010
dc.identifier.citationKonu, J., Chivers, T., & Tuononen, H. (2010). Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions, [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen−Chalcogen Bonded Dimers and a Novel Selone. <i>Chemistry - A European Journal</i>, <i>16</i>(43), 12977-12987. <a href="https://doi.org/10.1002/chem.201001699" target="_blank">https://doi.org/10.1002/chem.201001699</a>
dc.identifier.otherCONVID_20145369
dc.identifier.otherTUTKAID_43889
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47794
dc.description.abstractThe lithium salts of the chalcogenocarbonyl dianions [(E)C(PPh2S)2]2− (E=S (4 b), Se (4 c)) were produced through the reactions between Li2[C(PPh2S)2] and elemental chalcogens in the presence of tetramethylethylenediamine (TMEDA). The solid-state structure of {[Li(TMEDA)]2[(Se)C(PPh2S)2]}—[{Li(TMEDA)}24 c]—was shown to be bicyclic with the Li+ cations bis-S,Se-chelated by the dianionic ligand. One-electron oxidation of the dianions 4 b and 4 c with iodine afforded the diamagnetic complexes {[Li(TMEDA)]2[(SPh2P)2CEEC(PPh2S)2]} ([Li(TMEDA)]27 b (E=S), [Li(TMEDA)]27 c (E=Se)), which are formally dimers of the radical anions [(E)C(PPh2S)2]−. (E=S (5 b), Se (5 c)) with elongated central E[BOND]E bonds. Two-electron oxidation of the selenium-containing dianion 4 c with I2 yielded the LiI adduct of a neutral selone {[Li(TMEDA)][I(Se)C(PPh2S)2]}—[{LiI(TMEDA)}6 c]—whereas the analogous reaction with 4 b resulted in the formation of 7 b followed by protonation to give {[Li(TMEDA)][(SPh2P)2CSS(H)C(PPh2S)2]}—[Li(TMEDA)]8 b. Attempts to identify the transient radicals 5 b and 5 c by EPR spectroscopy in conjunction with DFT calculations of the electronic structures of these paramagnetic species and their dimers are also described. The crystal structures of [{Li(TMEDA)}24 c], [{LiI(TMEDA)}6 c]⋅C7H8, [Li(TMEDA)]27 b⋅(CH2Cl2)0.33, [Li(THF)2]27 b, [Li(TMEDA)]27 c, [Li(TMEDA)]8 b⋅(CH2Cl2)2 and [Li([12]crown-4)2]8 b were determined and salient structural features are discussed.
dc.language.isoeng
dc.publisherWiley
dc.relation.ispartofseriesChemistry - A European Journal
dc.subject.otherkalkogeenikarbonyylidianionit
dc.subject.otherchalcogenocarbonyl dianions
dc.titleSynthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions, [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen−Chalcogen Bonded Dimers and a Novel Selone
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511243775
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-24T07:15:13Z
dc.type.coarjournal article
dc.description.reviewstatuspeerReviewed
dc.format.pagerange12977-12987
dc.relation.issn0947-6539
dc.relation.numberinseries43
dc.relation.volume16
dc.type.versionacceptedVersion
dc.rights.copyright© 2010 Wiley-VCH Verlag GmbH & Co. This is a final draft version of an article whose final and definitive form has been published by Wiley. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.doi10.1002/chem.201001699


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record